Color photographic recording material

ABSTRACT

The present invention relates to new compounds having an active methylene group or phenolic hydroxyl group and therefore capable of being used as photographic color couplers. The new compounds contain at least one radical of a phosphoric acid diester, phosphonic acid diester, phosphoric acid diamide, phosphonic acid diamide, phosphoric acid ester-amide or phosphonic acid ester-amide.

This is a divisional of application Ser. No. 446,248, filed Feb. 27,1974, now U.S. Pat. No. 3,984,432

A large number of photographic colour coupling agents with an activemethylene group or phenolic hydroxyl group are known, for example fromthe following publications: German Offenlegungsschriften (orAuslegeschriften) 1,236,332, 1,522,414, 1,547,831 1,547,867, 1,547,868,1,804,167, 2,018,562, 2,039,970, 2,043,271, 2,123,448, 2,128,830,2,133,655, 2,152,336, 2,156,913, 2,160,167 and 2,216,578 (compare also1,113,138), U.S. Pat. Nos. 2,289,804, 2,600,788, 2,801,171, 2,895,826,2,908,573, 3,265,506 and 3,658,544 and British Pat. No. 1,290,423.

The invention relates to new compounds which can be used as photographiccolour coupling agents for the chromogen process and which possessparticularly good resistance to diffusion in photographic materials andexcellent solubility in the organic solvents known as solvents forcoupling agents. These new compounds with an active methylene group orphenolic hydroxyl group contain at least one radical of a phosphoricacid diester, phosphonic acid diester, phosphoric acid diamide,phosphonic acid diamide, phosphoric acid ester-amide or phosphonic acidester-amide. As a radical with an active methylene group, thesecompounds contain, for example, the radical of an acylacetylamine or ofa 5-pyrazolone, whilst as a radical with a phenolic hydroxyl group theycontain, for example, the radical of a phenol or naphthol. Preferredcompounds are those which contain the radical of a pivaloyl- orbenzoylacetylamine, of a 1-phenyl-5-pyrazolone, of a phenol or of a1-naphthol-2-carboxylic acid amide. On the other hand, preferredcompounds of this nature are those which contain at least one radical ofa phosphonic acid diester, that is to say the atom grouping ##STR1## Ascan be seen from the further comments, the new compounds can not only be4-equivalent coupling agents but also so-called two-equivalent couplingagents, which possess, in the coupling position, a radical which can besplit off during the colour coupling reaction.

Particularly preferred compounds are those of the formulae (1) to (23)which follow: ##STR2##

In the formulae, the individual symbols throughout have the samemeaning, and in particular denote the following: A₁ denotes a benzeneradical which can contain further substituents; A₂ denotes a benzeneradical which is not substituted further or a benzene radical which issubstituted further by at least one of the following substituents: amethyl group, a methoxy group, a phenoxy group or a chlorine atom; D₁denotes a benzene radical which is not substituted further or issubstituted further by at least one of the following substituents: ahalogen atom such as bromine or preferably chlorine, nitrile, a loweralkyl group (which can carry further substituents, such as a chlorineatom or a methoxy group), a lower alkoxy group, such as ethoxy ormethoxy, a lower alkylsulphonyl group, such as a methylsulphonyl group,or an acylamino group with 1 to 28 carbon atoms ("lower" groups are tobe understood as groups with 1 to 4 carbon atoms); D₂ denotes a benzeneradical which is optionally substituted further by one or more chlorineatoms, methyl groups or methoxy groups and/or a nitrile group; G₁denotes a benzene radical which can contain further substituents; G₂denotes a benzene radical which is not substituted further or issubstituted further by at least one of the following substituents:chlorine, methyl, methoxy or phenoxy; L₁ denotes an oxygen atom, analkylene group, a cyclohexane radical, a benzene radical or anaralkylene radical, such as ##STR3## L₂ denotes an oxygen atom, analkylene group with 1 to 3 carbon atoms, a benzene radical or anaralkylene radical; M₁ denotes a direct bond, an oxygen atom or one ofthe following atom groupings: Alkyl

(wherein the alkyl group ##STR4## contains at most 4 carbon atoms), --CO--HN--, --NH--OC--, --CO--O--, --CO--HN--benzene radical or --NH--OC--benzene radical; M₂ denotes a direct bond, an oxygen atom or one of theatom groupings --CO--HN--, --NH--OC--, --CO--HN--benzene radical and--NH--OC--benzene radical; (with regard to the groupings M-L [formulae(1) to (5), M₁ -L₁ or M₂ -L₂ ] it should be noted that M cannotrepresent oxygen, --CONH-- or --NH--CO if L represents an oxygen atom,and n in the formula (3) can be 1 or 2 if M₂ is a --CO--HN--benzeneradical or --NH--OC--benzene radical, but must be 1 if M₂ represents adirect bond, an oxygen atom, a --CO--HN-- group or --NH--OC-- group; inthe --CO--NH--benzene radicals and the --NH--OC--benzene radicals, if nis 2, the two --L-- should be in the 2,4-- or 3,5--position to--CO--HN-- or --NH--OC-- ); Q₁ denotes a radical which can be split offduring the colour coupling reaction; Q₂ denotes one of the radicals ofthe formulae --H, --Cl, R₁ denotes an alkyl group with 2 to 18 carbonatoms; R'₁ denotes an alkyl group with 2 to 8 carbon atoms or an alkoxygroup with 2 to 18 carbon atoms (the alkoxy groups can also form an--O--alkylene group conjointly with R₁); R₂ denotes an alkyl group with2 to 8 carbon atoms; R'₂ denotes an alkyl group with 2 to 8 carbon atomsor an alkoxy group with 2 to 8 carbon atoms; R₃ denotes one of thegroups ##STR5## R₄ denotes one of the groups --C₂ H₅ and --(CH₂)_(3--CH)₃ ; T₁ denotes an acylamino group, the nitrogen atom being bonded to thepyrazolone ring, especially a group which consists of a--NH--CO--benzene radical, a phenylureido group or a phenylamino groupwhich is not substituted further or is substituted further by at leastone of the following substituents: a halogen atom such as bromine orpreferably chlorine, a lower alkyl group such as ethyl or methyl, alower alkoxy group such as ethoxy or methoxy, and an acylamino groupwith 1 to 28 carbon atoms ("lower" groups are again to be understood asgroups with at most 4 carbon atoms); if n= 2, T₁ can also denote adirect bond; U₁ denotes a hydrogen atom, a chlorine atom, an alkyl groupwith at most 4 carbon atoms or an alkoxy group with at most 3 carbonatoms; V₁ denotes a hydrogen atom or a chlorine atom; W₁ denotes analkyl radical, preferably a radical with 1 to 32 carbon atoms, or abenzene radical, which can also carry substituents; W₂ denotes atertiary butyl radical, a benzene radical which is not substitutedfurther or a benzene radical which is substituted further by at leastone of the following substituents: an alkyl group with at most 4 carbonatoms, a methoxy group, an ethoxy group, a chlorine atom or abenzoylamino group; W₃ denotes a benzene radical which is notsubstituted further or is substituted further as indicated for W₂ ; Ydenotes a chlorine atom, a methyl group or a methoxy group; Y' denotes achlorine atom or a methyl group; k denotes one of the numbers 1 and 2; mdenotes one of the numbers 1 and 2; n denotes one of the numbers 1 and2; p denotes one of the numbers 1, 2 and 3; r denotes an integer havinga value of at least 1 and at most 18; s denotes one of the numbers 1 and2; t denotes one of the numbers 3 and 5.

The new colour coupling agents of the initially mentioned compositioncan be manufactured according to methods which are in themselves known.The following may be mentioned as special manufacturing processes forwhich patent protection is claimed.

1. An aminoaryl compound containing phosphorus is condensed with anacylacetic acid ester to give the acylacetic acid arylamide. Theaminoarylphosphorus compound which serves as the starting material issuitably manufactured by reacting a halogeno-nitro-aryl compound by theMichaelis-Arbuzov reaction with a trialkyl phosphite or triarylphosphite and then reducing the nitro group of the reaction product tothe amino group.

2. Colour coupling agents which contain at least one primary amino groupare condensed with carboxylic acid chlorides containing phosphorus.

3. A compound of this nature which contains a pyrazolone (5) ring issynthesised with the aid of an aminobenzene containing phosphorus or aphenylhydrazine containing phosphorus.

The methods of manufacture will still be explained in more detail later.

The known Michaelis-Arbuzov and Perkov reactions are particularlysuitable for introducing the phosphoric and phosphinic acid esterradicals or acid ester-amide radicals. See, for example, also thefollowing publications: Methoden der organischen Chemie (Methods ofOrganic Chemistry) (Houben-Weyl), volumes 12/1 and 12/2, Georg-ThiemeVerlag, Stuttgart 1963 and 1964; Symposium on Organo-PhosphorusCompounds held in Heidelberg, Germany, 20-22 May 1964; London,Butterworths 1964, pages 307-369, and literature mentioned therein;Organic Reactions, volume VI, John Wiley & Sons, Inc., New York 1951,pages 273- 338, and literature mentioned therein; OrganophosphorusChemistry, volumes 1- 3, The Chemical Society, London; Topics inPhosphorus Chemistry, volumes 1-4, Interscience Publishers, London-NewYork-Sydney.

In particular, coupling agents or suitable intermediate products can beobtained by the Michaelis-Arbuzov method by reaction of halogenderivatives, alcohols, aldehydes, unsaturated aldehydes or unsaturatedcarboxylic acids with trialkyl phosphites or triaryl phosphites. If theradical containing phosphorus is introduced into an intermediateproduct, the latter can, if necessary after suitable modification, beintroduced into the molecule which is to be coupled or be reacted togive a coupling agent.

A first method, in which the phosphonic acid ester radical is directlyintroduced into the coupling agent molecule, consists, for example, ofreacting a compound of the formula

    A--Hal

wherein A denotes the radical of a colour coupling agent and Hal denotesa halogen atom, preferably a bromine or iodine atom, with a trialkylphosphite or triaryl phosphite by a Michaelis-Arbusow reaction.

A further method for the direct introduction of the phosphonic acidester into the coupling agent molecule consists of the addition reactionof a dialkyl phosphite or trialkyl phosphite, or of a diaryl phosphiteor triaryl phosphite, with a double bond system present in a compound ofthe formula

    A--H

a third method, in which a phosphonic acid ester radical is initiallyintroduced into a reactive intermediate product, which is subsequentlylinked to the coupling agent molecule, consists, for example, ofreacting a trialkyl phosphite or triaryl phosphite, by aMichaelis-Arbuzov reaction, with a compound of the formula

Zw--Hal

wherein Zw represents an alkylene or arylene radical which issubstituted by a reactive atom, for example a further halogen atom, orby a reactive group, for example an activated ester group or an aminogroup. The compound thus obtained can then be reacted with a couplingagent, for example of the formula

A--nh₂, a--oh, a--cocl or A--NCO,

for example according to known methods.

A variant of this method is to modify the phosphorus containing reactiveintermediate product yet further before the reaction with a suitablecoupling agent molecule, for example by means of the following knownreactions at substituents which are present: ##STR6##

A fourth method for the preparation of coupling agents according to theinvention is to use an intermediate product obtained, for example, by aMichaelis-Arbuzov reaction between a trialkyl phosphite or triarylphosphite and a compound of the formula Zw' -Hal, wherein Zw' has themeaning of Zw, directly or after suitable modification, for thesynthesis of the actual coupling agent molecule, for example also of anacylacetanilide or of a pyrazolone ring. Such syntheses are described,inter alia, in: German Auslegeschriften 1,101,429, 1,237,580 and1,547,867, German Offenlegungsschriften 1,670,601, 1,797,083, 2,042,920,2,042,921, 2,042,922, 2,128,830, 2,156,913 and 2,162,899, or in J. Am.Chem. Soc 71, 983 (1949).

A particular embodiment of this method consists of reacting a nitroarylcompound containing halogen, for example a compound of the formula##STR7## in a Michaelis-Arbuzov reaction with a trialkyl phosphite ortriaryl phosphite, reducing the nitro group in the usual manner to theamino group and condensing the phosphorus-containing amino compound thusobtained with an acylacetic acid ester to give an acylacetic acidanilide.

It has hitherto been considered that the Michaelis-Arbusoz Arbusowreaction was not generally applicable to a halogen compound containingnitro groups. On this topic see, for example, Accounts of ChemicalResearch 5, 300 (1972) and Proc. chem. Soc. 1962, 361, Isvest. Akad.Nauk, S.S.S.R., Otdel Chim. Nauk, 1950, 56 and Doklady Akad. Nauk,S.S.S.R., 59, 1301 (1948).

The phosphonic acid ester radical can also be introduced by reaction ofa coupling agent, for example of the formula

    A-- NH.sub.2 or A-- OH

with a phostonate.

One method for introducing a phosphoric acid ester radical ischaracterised, for example, by reacting a phosphoric acid halide of theformula ##STR8## with a coupling agent molecule containing hydroxyl,mercapto or amino groups, or with an intermediate product or saltsthereof. In an analogous manner it is also possible to introduce, forexample, diaminophosphoryl radicals.

A further method for introducing the phosphoric acid ester radicalconsists, for example, of reacting an acid of the formula ##STR9## or asalt thereof with a coupling agent molecule containing a reactivehalogen atom or an aziridine grouping, or with a suitable intermediateproduct.

The so-called Perkov reaction of α-halogenocarbonyl compounds or theirvinyl homologues or of α-halogenonitro compounds with phosphites, isalso particularly suitable for the introduction of the phosphoric acidester radical.

Reaction of phosphorus oxychloride with coupling agent molecule(s), orintermediate products, containing hydroxyl groups givesdichlorophosphates which subsequently lead directly or via thecorresponding acid to diphosphoric acid esters or triphosphoric acidesters, diphosphoric acid amides or ester-amides. On this topic see, forexample, J. Chem. Soc., Perkin Trans., I 1972, 4, 583-86. Couplingagents, or intermediate products, containing hydroxyl groups can also becondensed with an orthophosphoric or polyphosphoric acid, withelimination of water, after which the resulting phosphoric acidderivative can be esterified.

There now follows a list of compounds from which the colour couplingagents of the composition mentioned initially can be derived by one ormore of the abovementioned methods.

The parts of the molecule of the compounds according to the inventionwhich contain the phosphoric acid radicals or phosphonic acid radicalsare derived, for example, from compounds of the following formulae:##STR10##

The phosphonic acid radicals and phosphoric acid radicals of thecompounds according to the invention are derived, for example, fromcompounds of the following formulae: ##STR11##

The phosphonic acid radicals of the compounds according to the inventionare preferably derived from compounds of the following formulae:##STR12##

The alkoxy groups --O--R₁ and --R' ₁ and further radicals which arepossible in place of these alkoxy groups are derived, for example, fromthe following hydroxy compounds: methanol, 1-propanol, 1-hexanol,1-decanol, 1 -tetradecanol, 1-octadecanol, 2-propanol, 2-octanol, 2-methyl-2-propanol, 3-chloro-1-propanol, 3-methoxy-1-butanol, benzylalcohol, 2-phenyl-ethanol, oleyl alcohol, 3-fluorophenol,2-chlorophenol, 4-methoxyphenol, 2-amino-4-iodophenol,2,4,5-trimethyl-phenol, 4-tert.-butoxyphenol, ethanol, 1-butanol,1-octanol, 1-dodecanol, 1-hexadecanol, 1-hexaeicosanol, 2-butanol,3-octanol, 2-ethyl-1-hexanol, 3-bromo- 1-propanol, cyclohexanol,1-phenyl-ethanol, allyl alcohol, α-3,7-dimethyl- 1,6-octadien-3-ol,2-methylphenol, 3-methylphenol, 4-methylphenol, 4-bromo-2-nitrophenol,3-dimethylaminophenol, 3-acetylaminophenol, ethylene glycol, ethyleneglycol monoisopropyl ether, ethylene glycol monophenyl ether, ethyleneglycol monomethyl ether, ethylene glycol mono-4 -chlorophenyl ether,1,2-propanediol, 1,3-propanediol, 1,3 -butanediol, 1,4-butanediol and2-mercaptoethanol.

The compounds according to the invention are outstandingly suitable foruse in light-sensitive silver halide emulsion layers of single-layer ormulti-layer materials for colour photography. However, it is notessential that the coupling agents should be incorporated into thelight-sensitive silver halide emulsion layers; rather, it is alsopossible to accommodate them in a light-insensitive or light-sensitivebinder layer which adjoins a light-sensitive silver halide emulsionlayer.

The coupling agents according to the invention can be incorporated intoa silver halide emulsion or into another binder mixture according to oneof the known methods. Appropriately, the following procedures are usedfor this purpose:

(a) Dissolving the coupling agent in a sparingly water-soluble organicsolvent of low volatility (boiling point, for example, above 200°C.) anddispersing the coupling agent solution directly in a photographicemulsion or dispersing the coupling agent solution beforehand in anaqueous medium and subsequently adding the dispersion to a photographicemulsion. Di-n-butyl phthalate, tricresyl phosphate, N,N-diethylcaproicacid amide, lauric acid dimethylamide, dibutylsulphone orN,N-dibutylurea are examples of such organic solvents.

On this topic see, for example, U.S. Patent Specifications 2,304,939,2,304,940 and 2,322,027.

(b) Dispersing the couping agent according to the invention in solventsof the so-called natural resin type, that is to say, for example, insolvents of the nature known from U.S. Pat. Spec. No. 2,284,879.

(c) A relatively water-insoluble low-boiling solvent is used as in thecase of (a) but is intended to be removed during one of the last stages.Ethyl acetate, methylene chloride, chloroform and cyclohexanone are usedas such solvents.

(d) A water-miscible organic solvent is used, which can be removedduring one of the last states or can remain in the photographicmaterial. Examples of such organic solvents are dimethylformamide,dimethylsulphoxide, N-methylpyrrolidone, methanol and ethanol.

With regard to (c) and (d) see, for example, U.S. Pat. Spec. Nos.2,801,170, 2,801,171 and 2,749,360.

(e) Heating and fusing the coupling agent without using an organicsolvent and dispersing the fused coupling agent directly in aphotographic emulsion or in an aqueous medium. This procedure issuitable for coupling agents melting below 85° C.

In some cases, the organic solvents mentioned under (a), (b), (c) and(d) can be mixed in order to obtain a good dispersion of the couplingagent.

(f) Finally, the coupling agents can also be dissolved in solutions ofpolymerisable monomers, after which the monomers are polymerised, forexample in the presence of gelatine, giving dispersions of the colourcoupling agents in the polymers. On this matter, reference may be made,for example, to the process known from U.S. Patent Spec. No. 2,825,382.

To prepare a photographic emulsion layer it is furthermore also possibleto use one or more coupling agents of the formula (1) together with aknown coupling agent. Suitable light-sensitive emulsions are emulsionsof silver halides such as silver chloride, silver bromide or mixturesthereof, optionally containing a small amount - up to 10 mol % - ofsilver iodide, in one of the customary hydrophilic binders such as aprotein, especially gelatine, polyvinyl alcohol, polyvinylpyrrolidone,cellulose derivatives, such as carboxyalkylcellulose, especiallycarboxymethylcellulose, or derivatives of alginic acid. The nature ofthe photographic silver halides is immaterial in relation to theinvention.

The emulsions can also be chemically sensitised, for example by additionof compounds containing sulphur, for example allyl isothiocyanate, allylthiourea, sodium thiosulphate and the like, during the chemicalripening. Other chemical sensitisers which can be used are reducingagents, for example the tin compounds described in Belgian Patent Specs.Nos. 493,464 or 568,687, and also polyamines such as diethylenetriamine,or aminomethanesulphinic acid derivatives, for example according toBelgian Pat. Spec. No. 547,323.

Further suitable chemical sensitisers are noble metals or noble metalcompounds such as gold, platinum, palladium, iridium, ruthenium orrhodium. This method of chemical sensitisation is described in thearticle by R. Koslowsky, Z. Wiss. Phot. 46, 65-72, (1951).

It is, furthermore, possible to sensitise the emulsions withpolyalkyleneoxy derivatives, for example with a polyethylene oxide ofmolecular weight between 1,000 and 20,000, or with condensation productsof alkylene oxides and aliphatic alcohols, glycols, cyclic dehydrationproducts of hexitols, alkyl-substituted phenols, aliphatic carboxylicacids, aliphatic amines, aliphatic diamines and amides. The condensationproducts have a molecular weight of at least 700, and preferably of morethan 1,000. To achieve special effects, these sensitisers can of coursealso be used in combination, as described in Belgian Pat. No. Spec.537,278 and in British Pat. Spec. No. 727,982.

The emulsions containing colour coupling agents can furthermore containspectral sensitisers, for example the customary monomethine orpolymethine dyestuffs, such as cyanines, hemicyanines, streptocyanines,merocyanines, oxonols, hemioxonols, styryl dyestuffs or others, and alsotrinuclear or polynuclear methine dyestuffs, for example rhodacyaninesor neocyanines. Such sensitisers are described, for example, in the workby P.M. Hamer "The Cyanine Dyes and Related Compounds", IntersciencePublishers John Wiley and Sons, 1964.

However, the invention is not restricted only to colour-photographicmaterials with several different spectrally sensitised silver halideemulsions but also relates to colour-photographic materials whichcontain mixed grain emulsions.

The emulsions can contain the customary stabilisers, such as, forexample, homopolar or salt-like compounds of mercury with aromatic orheterocyclic rings, such as mercaptotriazoles, simple mercury salts,sulphonium-mercury double salts and other mercury compounds. Furthersuitable stabilisers are azaindenes, preferably tetraazaindenes orpentaazaindenes, especially those substituted by hydroxyl or aminogroups. Such compounds are described in the article by Pirr, Z. Wiss.Phot. 47, 2-58 (1952). Further suitable stabilisers are, inter alia,heterocyclic mercapto compounds, for example phenylmercaptotetrazole,quaternary benzthiazole derivatives, benztriazole and the like.

The silver halide emulsions can also contain yet further photographicauxiliaries, for example coating auxiliaries, such as lubricants andwetting agents, or antistatic agents.

The emulsions can be hardened in the usual manner, for example by meansof metal salts such as zirconyl sulphate or chromium triacetate, or bymeans of organic compounds such as formaldehyde, halogen-substitutedaldehydes which contain a carboxyl group, such as mucobromic acid,diketones, dialdehydes, methanesulphonic acid esters, epoxides,heterocyclic compounds, especially azines, such as triazines, orpyrimidines with suitable removable groups, such as halogen atoms,alkoxy groups, alkylsulphonyl groups or groups with a quaternarynitrogen atom, aziridine compounds or compounds which contain a doublebond activated by a --CO-- or --SO₂ -- group, such as bis-acrylamidesand the like.

The new coupling agents react very well with the oxidation product ofall customary developers of the type of p-phenylenediamine such as, forexample, N,N-diethyl-p-phenylenediamine,N,N-diethyl-3-methyl-p-phenylenediamine,4-amino-3-methyl-N-ethyl-N-β(-methanesulphenamide)ethylaniline,N-ethyl-N(β-hydroxyethyl)-p-phenylenediamine,N-ethyl-N-β-hydroxyethyl-3-methyl-p-phenylenediamine andN-butyl-N-δ-sulphobutyl-p-phenylenediamine. Further usable colourdevelopers are described, for example, in J. Am. Chem. Soc. 73,3000-3025 [1951].

The same also applies to the case of the new coupling agents being usedin the form of phenylazo derivatives (mask coupling agents for negativematerials, see U.S. Patent Spec. No. 2,449,966).

In addition to the said developer compounds, the colour developers usedfor developing colour-photographic recording materials according to theinvention can also contain compounds which control the developingprocess, such as, for example, citracinic acid and the like. Inaddition, a durable colour image is obtained with a colour-photographicrecording material containing a coupling agent according to theinvention if a UV absorber is incorporated into the material, forexample a benzophenone compound such as4-phenyl-2'-hydroxy-4'-octyloxy-benzophenone, a triazole compound, forexample 2-(2'-hydroxy-3', 5'-di-tert.-butyl-or-di-tert.-amyl-phenyl)benztriazole, or a resorcinyl-triazine compound,such as 2 -phenyl-4,6-di[2'-hydroxy- 4' -(ω-carboethoxy-pentyloxy)]1,3,5-triazine.

The material according to the invention can also contain an opticalbrightener, for example a stilbene derivative.

It is also possible to employ the colour coupling agents according tothe invention as so-called single developer-coupling agents in a colourdeveloping bath, instead of employing them in photographic layers. Thecolour-photographic material employed in that case then preferably doesnot contain a built-in colour coupling agent in at least one of thesilver halide emulsion layers present. Such processes are described, forexample, in the following patent specifications: U.S. Pat. Specs. No.2,113,329, 2,252,718, 2,343,703 and 3,002,836, Belgian Pat. Spec. No.672,255, German Auslegeschrift 1,176,478, German Offenlegungsschrift2,062,350 and British Patent Spec. No. 680,488.

To manufacture the recording materials, it is furthermore possible touse customary known layer carriers, for example films of cellulosenitrate, cellulose acetate, polyvinyl acetal, polystyrene, polyethyleneterephthalate, polyethylene and polypropylene, but also layer carriersof paper, glass and the like. The layer carriers can furthermore alsoconsist of paper or some other fibrous material which is provided with ahydrophobic surface which is waterrepellent and neither absorbs noradsorbs water. Layer carriers with a hydrophobic surface can furthermorecarry hydrophobic resin layers which have been subjected to electronirradiation, as is known, for example, from British Pat. Spec. Nos.971,058 and 1,060,526, and U.S. Pat. Spec. Nos. 2,864,755 and 2,864,756,in order to improve the adhesion of layers of hydrophilic colloid. Suchresin layers can optionally also be used in the form of self-supportinglayers. Typical layer carriers with suitable hydrophobic surfaces are,for example, layer carriers of polyethylene terephthalate films, whichhave been irradiated with electrons in such a way that they have acontact angle of less than 45° (compare U.S. Pat. Spec. No. 3,220,842),or which have an electron-irradiated surface carrying a chromium halide(compare U.S. Pat. Spec. No. 3,117,865), or which are layer carriers ofpaper possessing a hardened gelatine layer which has been irradiatedwith electrons, as is known, for example, from Belgian Pat. Spec. No.671,661.

The layer carriers can optionally contain customary known additives, forexample pigments, for example titanium dioxide and/or antistaticcompounds, as is known, for example, from U.S. Pat. Spec. No. 3,253,922.Colour-photographic recording materials of particular importance arethose which consist of at least 3 superposed emulsion layers ofdifferent spectral sensitisation. To manufacture such recordingmaterials, the layer carrier can first be coated with, for example, alayer sensitive to red, then with a layer sensitive to green and finallywith a layer sensitive to blue, with or without a Carey-Lea filter layerbetween the layer sensitive to blue and the layer sensitive to green.The three layers of different colour sensitisation can however also besuperposed in a different sequence except that the Carey-Lea filterlayer must not be located above the layer sensitive to blue.Advantageously, the light-sensitive layers are located on the same sideof the layer carrier. The recording material can optionally possessintermediate layer and/or covering layers, in a customary known manner.

The components according to the invention can be employed either in thenegative-positive process or in the reversal process.

The coupling agents according to the invention are above alldistinguished by excellent solubility and a low tendency to crystallisein organic solvents, especially in water-immiscible solvents of highboiling point such as, for example, tricresyl phosphate isomer mixtureor dibutyl phthalate.

In addition, they have excellent diffusion resistance in photographiclayers, both during the casting process and during photographicprocessing.

A particular advantage of the ballast groups containing phosphorus isthat in comparison to long-chain or branched hydrophobic alkyl radicals,they give substantially improved hydrophilic properties. This expressesitself, inter alia, by a high coupling activity. With regard to theadvantages of hydrophilic groups in oil-soluble coupling agents, seealso German Offenlegungsschrift 1,958,303.

The combination of excellent solubility in organic solvents andexcellent diffusion-resistance, on the one hand, with good compatibilitywith water, on the other, is a particularly surprising unforeseeableproperty of the coupling agents according to the invention. A furtheradvantage of the coupling agents according to the invention resides inthe fact that they are easy to manufacture and that the requisitephosphorus-containing starting products are readily accessible. Incolour development, the new coupling agents give colour images ofexcellent fastness to light and advantageous spectral absorption,suitable for photographic applications.

The colour-photographic material which is manufactured using such a newcoupling agent is therefore characterised by good photographicproperties, good colour reproduction, adequate stability before andafter the treatments, and ease of manufacture.

As can be seen from Table A which follows, the compounds according tothe invention display a substantially greater solubility in oil (at 20°C.) than do the known coupling agents.

                                      TABLE A                                     __________________________________________________________________________                                                          Solubility in g                                                               per g of tri-           Compound                                    Described in                                                                            cresyl                  __________________________________________________________________________                                                          phosphate               DT-OS 1,522,414                             1.2                               DT-OS 2,039,970                             1                                 DT-OS 1,804,167                             1                                 DT-OS 2,216,578                             2                                 Table I, No. (109)                          The present                                                                             > 5                                                                 description                       Table I, No. (128)                          The present                                                                             > 5                                                                 description                       Table I, No. (135)                          The present                                                                             > 5                                                                 description                       US-PS 2,801,171 Coupling agent No. (4)      0.4                               US-PS 2,908,573  Coupling agent of the formula 2                                                                          0.7                               GB-PS 1,290,423 Coupling agent of the formula (15)                                                                        0.7                               Example, formula (701)                      The present                                                                             Miscible in all                                                     description                                                                             proportions             US-PS 2,600,788 Coupling agent of the formula (7)                                                                         0.6                               US-PS 2,908,573 Coupling agent of the formula (7)                                                                         0.3                               GB-PS 1,290,423 Coupling agent of the formula (9)                                                                         0.4                               Table II, No. (231)                         The present                                                                             Miscible in all                                                     description                                                                             proportions             Table II, No. (236)                         The present                                                                             Miscible in all                                                     description                                                                             proportions             Table II, No. (240)                         The present                                                                             Miscible in all                                                     description                                                                             proportions             Table II, No. (243)                         The present                                                                             Miscible in all                                                     description                                                                             proportions             Table II, No. (248)                         The present                                                                             Miscible in all                                                     description                                                                             proportions             Table II, No. (251)                         The present                                                                             Miscible in all                                                     description                                                                             proportions             Table II, No. (266)                         The present                                                                             Miscible in all                                                     description                                                                             proportions             __________________________________________________________________________

MANUFACTURING EXAMPLES EXAMPLE 1

2.8 g of 3-(p-aminophenyl)-phosphonic acid diethyl ester (manufacturedaccording to JACS, 81, 3026, [1959]) and 2.7 g of benzoylacetic acidmethyl ester are warmed with 70 mg of sodium ethylate in 15 ml ofabsolute xylene isomer mixture to 125° C. for 31/2hours and the methylalcohol formed is distilled off. After recrystallisation from ethylacetate and acetone/ether, 0.9 g of pure coupling agent of the formula(101) of Table I is obtained in the form of a white powder of meltingpoint 99°- 101° C.

The compounds of the formulae (102), (103), (113), (114), (115), (116),(117), (119), (124 ) and (125) of Table I are manufactured analogously.

EXAMPLE 2

10.4 g of 3-bromo-propane-phosphonic acid diethyl ester (manufactured ina known manner by heating 1,3 -dibromopropane with triethyl phosphiteand distilling off the ethyl bromide formed) and 15.2 g ofN-methyl-3-nitroaniline in 50 ml of methyl ethyl ketone are warmed with13 g of N-ethyl-diisopropylamine for 20 hours under reflux. Afterseparating the reaction mixture on a chromatography column (silica gel;chloroform as the eluant), 9.9 g of pure3-(N-methyl-N-3'-nitro-phenylamino) propane-phosphonic acid diethylester are obtained in the form of an orange-coloured oil.

9.9 g of this intermediate product, in 100 ml of ethanol, arehydrogenated with 0.5 g of palladium on active charcoal at roomtemperature and normal pressure in the usual manner, until theabsorption of hydrogen has ceased.

After separating off the catalyst, distilling off the ethanol andtreating the residue with 2 N sodium hydroxide solution and chloroform,5.4 g of 3-(N-methyl-N-3'-amino-phenylamino) propane-phosphonic aciddiethyl ester are obtained as a light brown oil.

The condensation with benzoylacetic acid methyl ester is carried out asindicated in Example 1.

The compound of the formula (104) is obtained in the form of a lightbrown resin, in a yield of 32%.

EXAMPLE 3

25.9 g of bromoacetic acid 3-nitrophenylamide and 37.5 g of tributylphosphite in 150 ml of pure xylene isomer mixture are stirred undernitrogen for 30 minutes at 130° C. The residue obtained after distillingoff the xylene and the excess tributyl phosphite at 1 mm Hg gives, afterrecrystallisation from chloroform/hexane, 29.5 g of pure3-nitro-phenylcarbamoyl-methane-phosphonic acid dibutyl ester of meltingpoint 80°- 81° C. in the form of fine white needles.

Reduction of the nitro group according to Example 2 and condensationwith pivaloylacetic acid ethyl ester analogously to Example 1 gives, ingood yield, the coupling agent of the formula (105 ) in the form of acolourless, highly viscous oil.

The compounds of the formulae (106) and (109) are obtained analogously.

EXAMPLE 4

83 g of 3-nitrobenzoyl chloride in 150 ml of acetonitrile are addeddropwise to a solution of 105 g of 2-aminopropane-2-phosphonic aciddiethyl ester and 45 g of triethylamine in 300 ml of acetonitrile at 0°C., with good stirring. After completion of the addition, the mixture isstirred for a further 3 hours at 0° C.; it is then filtered and thesolvent is distilled off in vacuo. The residue is purified by extractionby shaking with ether and aqueous 2 normal sodium carbonate solution. 99g of 2-(3'-nitrobenzamido)propane-2-phosphonic acid diethyl ester ofmelting point 95°-96° C. are obtained. This product is reduced withhydrogen as indicated in Example 2.

A solution of 5.6 g of 3-nitrobenzoyl chloride in 30 ml of acetonitrileis added dropwise to a mixture of 10.4 g of the amino compound obtainedabove and 3 g of triethylamine in 100 ml of acetonitrile at 0° C., withgood stirring. Thereafter, the mixture is stirred for a further hour at0° C. and after distilling off the acetonitrile, the residue isdissolved in chloroform and purified by successive extraction by shakingwith 2 N hydrochloric acid, water and 2 N ammonia.

11.5 g of 2-[3'-(3"-nitrobenzamido)benzamido] propane- 2-phosphonic aciddiethyl ester of melting point 120°- 121° C. are obtained.

After reduction of the nitro group and subsequent condensation withbenzoylacetic acid methyl ester according to Example 1, the couplingagent of the formula (107) is obtained in good yield as a yellowishpowder of melting point 93° - 95° C. The compounds of the formulae (126), (136 ), (137) and (143 ) are manufactured analogously, employing theanilines from Example 1 in place of 2-(3'-aminobenzamido)propane-2phosphonic acid diethyl ester.

If 2-(3'-aminobenzamido)propane-2-phosphonic acid diethyl ester iscondensed directly with benzoylacetic acid methyl ester, analogously toExample 1, the compound of the formula (108) is obtained in excellentyield, in the form of a white powder of melting point 158° - 160° C.

The compounds of the formulae (110), (111), (118), (127), (128), (131),(133), (134), (135), (139) and (140) are manufactured analogously.

EXAMPLE 5

1.34 g of 3-amino-benzoylacetic acid 2'-methoxy-5'-methyl-phenylamide,prepared by condensation of 3-nitro-benzoylacetic acid methyl ester with2-methoxy-5-methylaniline and subsequent reduction of the nitro group,and 1.6 g of the acid chloride from Example 15, in 15 ml ofN-methylpyrrolidone, are stirred for 3 hours at room temperature. Afterevaporation under 1 mm Hg and purification by column chromatography(silica gel), 1.5 g of the compound (112) are obtained in the form of alight yellow resin. The compounds (120) and (121) are preparedanalogously.

EXAMPLE 6

3.4 g of the amino compound prepared according to Example 15, 2.1 g ofbenzoylacetic acid methyl ester and 0.1 ml of sym.-collidine in 30 ml ofp-xylene are warmed for one and a half hours to 140° C. and the methanolformed is distilled off. After purification through a chromatographycolumn, the compound of the formula (122) is obtained in the form of alight yellow resin.

The compound of the formula (123 ) is obtained analogously.

EXAMPLE 7

41.9 g of t-butane-phosphonic acid dichloride are dissolved in 300 ml ofacetonitrile and a suspension of 33 g of sodium phenolate in 150 ml ofacetonitrile is added at -15° C. in such a way that the temperature doesnot exceed -12° C. After completion of the addition, the temperature isallowed to rise slowly to 20° C. and after 3 hours a suspension of 46 gof sodium 4-nitrophenolate in 150 ml of acetonitrile is added and themixture is warmed to 60° C. for 2 hours. After distilling off thesolvent, the residue is hydrogenated in isopropanol with palladium oncharcoal as the catalyst (1 atmosphere). After purifying the crudeproduct by extraction with ether and of the ether extract with hexane,30 g of t-butanephosphonic acid 4-aminophenyl-(phenyl) ester of meltingpoint 105° C. are obtained. Condensation with benzoylacetic acid methylester in accordance with the method indicated in Example 6 gives thecompound of the formula (129), of melting point 148° C., in excellentyield.

The compound of the formula (130) is prepared analogously.

EXAMPLE 8

31 g of diisoamyl phosphite are slowly added dropwise at 80° C. to asuspension of 3.1 g of sodium in 150 ml of absolute toluene. Aftercompletion of the reaction, the suspension thus obtained is slowly addedto a solution of 30 g of 3-phenyl-propyl bromide at 80° C., whilststirring well. After 3 hours, the reaction mixture is centrifuged, thesupernatant solution is evaporated and the residue is distilled under avacuum of 0.2 mm Hg. At 158° C., 18 g of pure 3-phenylpropane-phosphonicacid diisoamyl ester pass over. After nitration and reduction (compareExample 1 ), 15.5 g of 3-(4'-aminophenyl)-propane-phosphonic aciddiisoamyl ester are obtained.

The condensation with 4-chloro-benzoylacetic acid methyl ester inaccordance with the method indicated in Example 6 gives the couplingagent of the formula (132), of melting point 116° C., in good yield.

EXAMPLE 9

20 g of n-butanephosphonic acid n-butyl ester chloride are addeddropwise to a suspension of 14.3 g of sodium 3-nitrophenolate in 170 mltoluene at 20° C. After 4 hours, the mixture is filtered, the filtrateis evaporated and the residue is distilled in vacuo at 0.1 mm Hg. 16 gof n-butanephosphonic acid n-butyl-(3-nitrophenyl) ester are obtained.After reduction with hydrogen and palladium on charcoal, in isopropanol,at 1 atmosphere pressure, 13.8 g of n-butanephosphonic acidn-butyl-(3-aminophenyl) ester are obtained.

A solution of 16 g of 4-nitrophenylacetyl chloride in 30 ml of benzeneis added dropwise to a solution of 11.5 g of n-butanephosphonic acidn-butyl-(3-aminophenyl) ester and 6 g of triethylamine in 50 ml ofbenzene at 20° C. After 40 hours, the mixture is filtered and thefiltrate is purified by extraction by shaking with potassium bicarbonatesolution and hydrochloric acid. 9.3 g of n-butanephosphonic acidn-butyl-[3-(4'-nitrophenyl-acetamido)phenyl] ester are obtained. This isreduced as indicated in Example 7 . After the condensation with2-chlorobenzoylacetic acid ethyl ester in accordance with the methodindicated in Example 6, a crude product is obtained, from which the pureproduct of the formula (138 ) is obtained by purification by columnchromatography.

EXAMPLE 10

29 g of n-butanephosphonic acid n-butyl ester chloride are addeddropwise to a solution of 20 g of 3-nitroaniline and 14.1 g oftriethylamine in 300 ml of acetonitrile at 0° C. After 20 hours themixture is evaporated, the residue is suspended in 300 ml of ether, themixture is acidified with hydrochloric acid in ether and filtered, andthe filtrate is evaporated. 33 g of n-butanephosphonic acid n-butylester 3-nitroanilide are obtained in the form of a yellow oil.

After reduction with hydrogen and acylation with2-chloro-5-nitro-benzoyl chloride in chloroform/triethylamine, andpurification by column chromatography, 7 g of n-butane-phosphonic acidn-butyl ester-3-(2'-chloro-5'-nitro-benzamido)-anilide are obtained. 4.7g of this compound are dissolved in 50 ml of glacial acetic acid at 20°C. 1.25 g of iron powder, 0.2 ml of water and a little iron-(II)sulphate are added thereto. The reaction mixture is warmed to 55° C.whilst stirring well and is kept at this temperature for 3 hours. Afterevaporation in vacuo, the residue is partitioned between 80 ml of 1normal sodium carbonate solution and 300 ml of chloroform. Thechloroform phase on evaporation gives 5.5 g of n-butanephosphonic acidn-butyl ester-3-(2'-chloro-5'-amino-benzamido)-anilide. Aftercondensation with benzoylacetic acid methyl ester in accordance withExample 6 and purification of the crude product by columnchromatography, the compound of the formula (141) is obtained in theform of a dark yellow resin.

EXAMPLE 11

A solution of 15 g of 4-nitro-benzoyl chloride in 100 ml of acetonitrileis added dropwise to a solution of 20 g of α-hydroxy-propanephosphonicacid dibutyl ester and 8 g of pyridine in 20 ml of acetonitrile at 0° C.After 16 hours the mixture is filtered, the filtrate is evaporated andthe residue is extracted with 200 ml of diethyl ether. Afterevaporation, and purification by column chromatography, 13 g of pureα-(4-nitro-benzoyloxy)-propanephosphonic acid dibutyl ester areobtained. This is reduced with hydrogen as indicated in Example 2. 12.5g of α-(4-amino-benzoyl-oxy)-propanephosphonic acid dibutyl ester areobtained. After condensation with o-methoxybenzoylacetic acid methylester according to Example 6, and purification by column chromatography,the compound of the formula (142 ) is obtained in the form of a yellowresin.

EXAMPLE 12

A solution of 10.3 g of 4-chloro-3-nitro-benzoyl chloride in 40 ml ofacetonitrile is added dropwise to a solution of 15 g of5-amino-1,3,3-trimethyl-cyclo-hexanephosphonic acid diisopropyl esterand 5 g of triethylamine in 250 ml of acetonitrile at -5° C. After 2hours, the temperature is allowed to rise to 20° C. and the mixture isstirred for a further 17 hours at this temperature. It is then stirredfor a further 4 hours, at 50° C. After evaporation, the residue ispartitioned between 300 ml of chloroform and 50 ml of water and thechloroform phase is successively extracted by shaking with 2 Nhydrochloric acid and 2 N sodium carbonate solution. After distillingoff the chloroform and recrystallising from ethyl acetate, 14.1 g of5-(3'-chloro-4'-nitro-benzamido)-1,3,3-trimethylcyclohexanephosphonicacid diisopropyl ester of melting point 174° C. are obtained.

11.2 g of this product, in a solution of 1.5 g of sodium and 3.3 g ofphenol in 200 ml of isopropanol, are allowed to react for 40 hours at50° C. After distilling off the isopropanol, the residue is dissolved inchloroform and the chloroform phase is washed with water until neutral.After distilling off the chloroform, 11.7 g of5-(3'-phenoxy-4'-nitro-benzamido)-1,3,3-trimethyl-cyclohexane-phosphonic acid diisopropyl ester areobtained in the form of a reddish-yellow oil.

This is reduced in isopropanol by means of hydrogen, as indicated inExample 2. 7.7 g of 5-(3'-phenoxy-4'-amino-benzamido)-1,3,3-trimethyl-cyclohexane-phosphonic acid diisopropyl ester areobtained in the form of a dark brown oil.

After condensation with 4-chlorobenzylacetic acid methyl ester inaccordance with Example 6 and purification by column chromatography, thecompound of the formula (144) is obtained in the form of a light yellowresin.

EXAMPLE 13

A solution of 5.5 g of 3-nitro-benzoyl chloride in 25 ml of acetonitrileis added dropwise to a solution of 11.4 g of 4-amino-benzenephosphonicacid di-n-hexyl ester and 3.7 g of triethylamine in 100 ml ofacetonitrile at 0° C. After one and a half hours, the mixture is allowedto warm up to 20° C. and is stirred for a further hour at thistemperature.

After distilling off the acetonitrile, the residue is extracted with 200ml of benzene, the benzene phase is successively washed with 50 ml of 2N sodium carbonate solution, 50 ml of 2 N hydrochloric acid and 50 ml ofwater and the benzene is distilled off apart from a small residue. Aftercompletion of crystallisation, the product is filtered off andrecrystallised from diethyl ether. 6.1 g of4-(3'-nitrobenzamido)-benzenephosphonic acid di-n-hexyl ester of meltingpoint 98° C. are obtained. After reduction with hydrogen andcondensation with 4-chlorobenzoylacetic acid methyl ester in accordancewith the method indicated in Example 6, the coupling agent of theformula (145) is obtained in good yield.

EXAMPLE 14

0.3 g of sulphuryl chloride is added dropwise at 20° C. to a solution of0.8 g of the compound of the formula (130) and 0.14 g of anhydroussodium acetate in 8 ml of glacial acetic acid. After 50 minutes, themixture is poured into 70 ml of ice water and the product is filteredoff and recrystallised from ethyl acetate. 0.4 g of the compound (146),of melting point 128° C., is obtained.

The compound of the formula (117) is prepared analogously.

The compounds of the formulae which follow are prepared according tomethods which are in themselves known, from the corresponding4-equivalent coupling agents (the corresponding compounds with hydrogenin the position marked with , in place of the substituents drawn). Withregard to methods of manufacture, compare DT-OS or DT-AS 1,236,332,2,043,271, 1,547,672 or 1,187,477. Next to the formula, the absorptionmaximum in nm is specified in each case (see footnote to Table I).##STR23##

                                      TABLE I                                     __________________________________________________________________________    For-                                                      Abs.                mula                                                      max. *              No. Structure                                             in                  __________________________________________________________________________                                                              [nm]                (101)                                                                             437                                                                       (102)                                                                             438STR24##                                                                (103)                                                                             429STR25##                                                                (104)                                                                             435STR26##                                                                (105)                                                                             436STR27##                                                                (106)                                                                             442STR28##                                                                (107)                                                                             444STR29##                                                                (108)                                                                             440STR30##                                                                (109)                                                                             442STR31##                                                                (110)                                                                             440STR32##                                                                (111)                                                                             440STR33##                                                                (112)                                                                             440STR34##                                                                (113)                                                                             434STR35##                                                                (114)                                                                             431STR36##                                                                (115)                                                                             435STR37##                                                                (116)                                                                             444STR38##                                                                (117)                                                                             445STR39##                                                                (118)                                                                             438STR40##                                                                (119)                                                                             436STR41##                                                                (120)                                                                             434STR42##                                                                (121)                                                                             434STR43##                                                                (122)                                                                             436STR44##                                                                (123)                                                                             436STR45##                                                                (124)                                                                             436STR46##                                                                (125)                                                                             436STR47##                                                                (126)                                                                             448STR48##                                                                (127)                                                                             444STR49##                                                                (128)                                                                             447STR50##                                                                (129)                                                                             440STR51##                                                                (130)                                                                             437STR52##                                                                (131)                                                                             442STR53##                                                                (132)                                                                             438STR54##                                                                (133)                                                                             436STR55##                                                                (134)                                                                             447STR56##                                                                (135)                                                                             445STR57##                                                                (136)                                                                             440STR58##                                                                (137)                                                                             425STR59##                                                                (138)                                                                             442STR60##                                                                (139)                                                                             441STR61##                                                                (140)                                                                             439STR62##                                                                (141)                                                                             438STR63##                                                                (142)                                                                             435STR64##                                                                (143)                                                                             440STR65##                                                                (144)                                                                             441STR66##                                                                (145)                                                                             449STR67##                                                                (146)                                                                             437STR68##                                                                (147)                                                                             436STR69##                                                                __________________________________________________________________________     * After colour developement of the coupling agents in a photographic          silver halide layer according to Use Example I                           

EXAMPLE 15

1.5 g of m-hydroxybenzoic acid methyl ester, 2.6 g of3-bromopropane-phosphonic acid diethyl ester prepared in the usualmanner from 1,3-dibromopropane and triethyl phosphite and 0.7 g ofanhydrous potassium carbonate in 20 ml of ethyl methyl ketone are heatedto the boil under reflux for 36 hours. The potassium bromide which hasseparated out is filtered off and the filtrate is evaporated to dryness,whereupon 2.9 g of ester of the formula ##STR70## are obtained in theform of a yellowish oil.

Saponification of 30 g of this ester in ethanolic sodium hydroxidesolution at 55° C. gives 25 g of acid of the formula ##STR71## in theform of a yellowish oil.

5 g of the carboxylic acid thus obtained, on reaction with thionylchloride in the usual manner, give 5 g of the acid chloride of theformula ##STR72## as a yellowish oil.

0.4 g of 1(2',4',6'trichlorophenyl)-3(4"aminobenzamido) 5-pyrazoloneobtained in a known manner is dissolved in 5 ml ofN-methyl-5-pyrrolidone and this solution is added to 0.4 g of acidchloride of the above formula. The reaction mixture is stirred for 1hour at room temperature and poured into a mixture of 25 ml of water and1.2 ml of 30% strength sodium hydroxide solution, the whole is stirredfor 15 minutes and filtered, and 40 ml of water and 5 ml of 36% strengthhydrochloric acid are added to the filtrate.

The product which has precipitated is filtered off, washed with wateruntil neutral and dried, and 0.6 g of coupling agent of the formula(201) is obtained in the form of a light beige powder of melting point120° C.

The remaining compounds of Table II are prepared analogously.

    TABLE II      ##STR73##          Abs. max in Formula[nm]*) (see No. R.sub.11 R.sub.12 footnote,     Table I)      (201)      ##STR74##      ##STR75##      432 + 542      (202)     ##STR76##      ##STR77##      434 + 535      (203)     ##STR78##      ##STR79##      434 + 539      (204)     ##STR80##      ##STR81##      434 + 534      (205)     ##STR82##      ##STR83##      434 + 542      (206)     ##STR84##      ##STR85##      434 + 542      (207)     ##STR86##      ##STR87##      434 + 540      (208)     ##STR88##      ##STR89##      434 + 546      (209)     ##STR90##      ##STR91##      436 + 540      (210)     ##STR92##      ##STR93##      434 + 543      (211)     ##STR94##      ##STR95##      434 + 543      (212)     ##STR96##      ##STR97##      434 + 544      (213)     ##STR98##      ##STR99##      434 + 537      (214)     ##STR100##      ##STR101##      432 + 540      (215)     ##STR102##      ##STR103##      434 + 540      (216)     ##STR104##      ##STR105##      432 + 546      (217)     ##STR106##      ##STR107##      435 + 538      (218)     ##STR108##      ##STR109##      436 + 542      (219)     ##STR110##      ##STR111##      436 + 542      (220)     ##STR112##      ##STR113##      434 + 544      (221)     ##STR114##      ##STR115##      436 + 538      (222)     ##STR116##      ##STR117##      434 + 544      (223)     ##STR118##      ##STR119##      440 + 534      (224)     ##STR120##      ##STR121##      440 + 534      (225)     ##STR122##      ##STR123##      440 + 532      (226)     ##STR124##      ##STR125##      439 + 534      (227)     ##STR126##      ##STR127##      438 + 532      (228)     ##STR128##      ##STR129##      438 + 533      (229)     ##STR130##      ##STR131##      440 + 532      (230)     ##STR132##      ##STR133##      434 + 544      (231)     ##STR134##      ##STR135##      434 + 545      (232)     ##STR136##      ##STR137##      434 + 541      (233)     ##STR138##      ##STR139##      441 + 530      (234)     ##STR140##      ##STR141##      434 + 540      (235)     ##STR142##      ##STR143##      440 + 532      (236)     ##STR144##      ##STR145##      436 + 541      (237)     ##STR146##      ##STR147##      432 + 536      (238)     ##STR148##      ##STR149##      440 + 530      (239)     ##STR150##      ##STR151##      440 + 532      (240)     ##STR152##      ##STR153##      434 + 544      (241)     ##STR154##      ##STR155##      434 + 541      (242)     ##STR156##      ##STR157##      436 + 542      (243)     ##STR158##      ##STR159##      434 +  544      (244)     ##STR160##      ##STR161##      434 + 542      (245)     ##STR162##      ##STR163##      434 + 542      (246)     ##STR164##      ##STR165##      440 + 532      (247)     ##STR166##      ##STR167##      436 + 540      (248)     ##STR168##      ##STR169##      436 + 541      (249)     ##STR170##      ##STR171##      442 + 532      (250)     ##STR172##      ##STR173##      434 + 537      (251)     ##STR174##      ##STR175##      436 + 540      (252)     ##STR176##      ##STR177##      440 + 532      (253)     ##STR178##      ##STR179##      440 + 540      (254)     ##STR180##      ##STR181##      438 + 540      (255)     ##STR182##      ##STR183##      438 + 536      (256)     ##STR184##      ##STR185##      438 + 534      (257)     ##STR186##      ##STR187##      430 + 537      (258)     ##STR188##      ##STR189##      550 + 580      (259)     ##STR190##      ##STR191##      548 + 583      (260)     ##STR192##      ##STR193##      440 + 535      (261)     ##STR194##      ##STR195##      440 + 535      (262)     ##STR196##      ##STR197##      440 +  536      (263)     ##STR198##      ##STR199##      440 + 534      (264)     ##STR200##      ##STR201##      440 + 536      (265)     ##STR202##      ##STR203##      436 + 537      (266)     ##STR204##      ##STR205##      436 + 540      (267)     ##STR206##      ##STR207##      436 + 536      (268)     ##STR208##      ##STR209##      438 + 540      (269)     ##STR210##      ##STR211##      438 + 540       (270)     ##STR212##      ##STR213##      438 + 544      (271)     ##STR214##      ##STR215##      440 + 532      (272)     ##STR216##      ##STR217##      438 + 540      (273)     ##STR218##      ##STR219##      430 + 547      (274)     ##STR220##      ##STR221##      430 + 546      (275)     ##STR222##      ##STR223##      440 + 538      (276)     ##STR224##      ##STR225##      440 +

EXAMPLE 16

Bromination of the compound of the formula (245) according to US-PS3,006,759 gives the compound of the formula ##STR226## Absorptionmaximum 434 + 542 nm.

EXAMPLE 17

14.2 g of sodium m-nitrophenolate and 22.8 g of 3-bromopropylphosphonicacid diethyl ester in 200 ml of methyl ethyl ketone are stirred for 6hours at 110° C. The mixture is cooled to room temperature, the sodiumbromide which has separated out is filtered off, the solvent isdistilled off and the residue is fractionated in a high vacuum.

21.0 g of nitro compound of the formula ##STR227## are obtained as ayellow oil of boiling point (0.3 mm Hg) 180°- 185° C.

Catalytic reduction of 43.0 g of the nitro compound at room temperatureunder normal pressure gives 36.5 g of amino compound of the formula##STR228## as a light yellow oil.

4.0 of 1-ethoxy-1-amino-acrylic acid ethyl ester hydrochloride aredissolved in 23 ml of methanol and this solution is added to 5.8 g ofamine of the above formula. The mixture is stirred for 24 hours at roomtemperature and evaporated to dryness, the residue is extracted with 50ml of benzene and the extract is concentrated. The residue consists of8.5 g of red-brown oil of the formula ##STR229## 4.4 g of this compoundand 1.1 g of phenylhydrazine in 10 ml of ethanol are stirred for 18hours at room temperature. The mixture is filtered and the residue isconcentrated and caused to crystallise by trituration with diethylether. Recrystallisation from benzene and from acetone gives 0.5 g ofpure coupling agent of the formula (401) (Table III) as a light yellowpowder of melting point 148° -150° C.

The compounds of the formulae (402) and (410) to (413) are preparedanalogously.

EXAMPLE 18

6.8 g of 3-methoxy-3-(2',4',6'-trichlorophenylhydrazino)-acrylic acidethyl ester and 5.7 g of compound of the formula ##STR230## in 5 ml ofglacial acetic acid are stirred for 3 hours at 100° C. under nitrogen.50 ml of ethanol are added, the mixture is cooled to 0° C. and theproduct which has crystallised out is filtered off.

After recrystallisation from ethanol, 1.7 g of coupling agent of theformula (403) are obtained as a yellow powder of melting point 162°-164° C.

The compounds of the formulae (404) to (409) are prepared analogously.

EXAMPLE 19

The compounds of the formulae (414) to (424) and (427) to (430) areprepared analogously to Example 15. The compounds (408) and (409) areprepared analogously to Example 17.

EXAMPLE 201-(3Nitro-2,4,6-trimethylphenyl)-3-(4-chloroanilino)-5-pyrazolone.

26.9 g (0.14 mol) of trimethoxypropionic acid ethyl ester (preparedaccording to DT-OS 2,042,920 ) are dissolved in 100 ml of absolutemethanol, 7 ml of glacial acetic acid are added and the mixture isheated to the boil. 23.4 g (0.12 mol) of3-nitro-2,4,6-trimethylphenylhydrazine (prepared according to DT-OS2,156,913) are introduced in portions into the mixture over the courseof 10 minutes. The mixture is stirred for a further 10 minutes at theboil and is allowed to cool whilst stirring. The orange crystals whichhave precipitated are filtered off, washed with a little methanol anddried (18 hours in vacuo at 50° C.). 14.4 g ofβ-methoxy-β-(3-nitro-2,4,6-trimethylphenylhydrazino)-acrylic acid ethylester of melting point 82° - 83° C. are obtained.

16.3 g (0.05 mol) of this compound are well mixed with 6.95 g (0.054mol) of p-chloroaniline and the mixture is stirred with 10.1 ml ofglacial acetic acid. The mixture is warmed to 50° C. for 4 hours and 50ml of absolute methanol are then added. The whole is allowed to coolwhilst stirring and the crystals are filtered off and rinsed with alittle methanol. After drying in vacuo at 70° C., 11.9 g of thepyrazolone, of melting point 263° - 265° C, are obtained.1-(3-Amino-2,4,6-trimethylphenyl)-3-(4-chloroanilino)-5 -pyrazolone.

7.5 g (0.02 mol) of the above nitropyrazolone are dissolved in 70 ml ofDMF and 15 ml of glacial acetic acid and 6 ml of H₂ O are added. Themixture is warmed to 40° C. under a N₂ atmosphere and 20 g of Fe powderare introduced. The reaction is allowed to take place for 8 hours at 40°C., 40 ml of methanol are added, and the mixture is filtered. Thefiltrate is poured into 700 ml of H₂ O and the product which hasprecipitated is filtered off. The filter residue is dissolved in 60 mlof hot methanol and allowed to crystallise. After filtering off thecrystals, and drying them at 70° C. in vacuo, 5.7 g of the aboveaminopyrazolone, of melting point 236° -237° C., are obtained.

Coupling agent of the formula No. 425, Table III

0.72 g (0.002 mol) of the above aminopyrazolone are dissolved in 10 mlof glacial acetic acid and the solution is mixed with 210 mg ofanhydrous sodium acetate. A solution of 0.73 g (0.0022 mol) of the acidchloride of the formula ##STR231## (prepared according to Example 15) in2.5 ml of glacial acetic acid is allowed to run in at 45° -50° C. Thereaction is allowed to take place for 2 hours at this temperature, thereaction mixture is poured into 100 ml of ice water and the product isfiltered off and washed thoroughly with H₂ O. The crude product is takenup in chloroform and precipitated with petroleum ether. After additionof a little H₂ O, the product solidifies. It is filtered off and driedin vacuo at 50° C. Yield: 200 mg. Melting point: 132° -138° C.

EXAMPLE 21 Coupling agent of the formula No. 426, Table III

This coupling agent is prepared analogously to Example 20. However,instead of the acid chloride used in Example 20, the acid chloride ofthe formula ##STR232## prepared analogously to Example 15 is employed.

A product of melting point 117° -127° C. is obtained.

    TABLE III      ##STR233##           Formula   Abs.max.*) No. R.sub.13 R.sub.14 in[nm]        (401)      ##STR234##      ##STR235##      429 + 524      (402)     ##STR236##      ##STR237##      430 + 534      (403)     ##STR238##      ##STR239##      424 + 526      (404)     ##STR240##      ##STR241##      425 + 530      (405)     ##STR242##      ##STR243##      428 + 526      (406)     ##STR244##      ##STR245##      426 + 530      (407)     ##STR246##      ##STR247##      429 + 527      (408)     ##STR248##      ##STR249##      426 + 530      (409)     ##STR250##      ##STR251##      426 + 330      (410)     ##STR252##      ##STR253##      438 + 532      (411)     ##STR254##      ##STR255##      428 + 532      (412)     ##STR256##      ##STR257##      430 + 528      (413)     ##STR258##      ##STR259##      428 + 533      (414)     ##STR260##      ##STR261##      430 + 530      (415)     ##STR262##      ##STR263##      426 + 532      (416)     ##STR264##      ##STR265##      426 + 528      (417)     ##STR266##      ##STR267##      428 + 528      (418)     ##STR268##      ##STR269##      430 + 530      (419)     ##STR270##      ##STR271##      427 + 532      (420)     ##STR272##      ##STR273##      428 + 529      (421)     ##STR274##      ##STR275##      430 + 528      (422)     ##STR276##      ##STR277##      426 + 530      (423)     ##STR278##      ##STR279##      430 + 530      (424)     ##STR280##      ##STR281##      427 + 532      (425)     ##STR282##      ##STR283##      430 +      530     ##STR284##      (426)     ##STR285##      ##STR286##      430 +      528     ##STR287##      (427)     ##STR288##      ##STR289##      431 + 538      (428)     ##STR290##      ##STR291##      430 + 537      (429)     ##STR292##      ##STR293##      430 + 538      (430)     ##STR294##      ##STR295##      430 +

EXAMPLE 22

2.6 g of 1-hydroxy-2-naphthoic acid phenyl ester and 2.9 g of3-(m-aminophenyl)-propoxy-phosphonic acid diethyl ester are warmed to130° - 140° C. over the course of 4 hours. The phenol split off isdistilled off in vacuo and the crude product is purified by columnchromatography on silica. 1.5 g of pure coupling agent of the formula(601) of Table IV are obtained in the form of a white powder of meltingpoint 104° - 107° C.

The compound of the formula (602) is prepared analogously. Melting point79° -81° C.

                                      TABLE IV                                    __________________________________________________________________________     ##STR296##                                                                                                               Abs.max.*)                        Formula No.                                                                           R.sub.15                                                                         R.sub.16                         in [nm]                           __________________________________________________________________________    (601)   H                                                                                704STR297##                                                        (602)   H                                                                                706STR298##                                                        __________________________________________________________________________

EXAMPLE 23

3.1 g of 3,5-di[3'-di-n-butoxy-phospho)-propoxy] benzoic acid chlorideand 1.0 g of 2-amino-4,6-dichloro-5-methyl-phenol (prepared according toDOS 2,216,804) in 20 ml of N-methyl-pyrrolidone are stirred for 3 hoursat room temperature. The reaction mixture is poured into 100 ml of waterand the emulsion is then extracted with 150 ml of ether. The organicphase is washed until neutral, dried and concentrated. The crude productis purified by column chromatography on silica. 1.0 g of light brown oilof the formula (701) ##STR299## is obtained. The cyan dyestuff preparedtherefrom according to Use Example I has an absorption maximum of 662nm.

USE EXAMPLES EXAMPLE I

0.3 mmol of coupling agent of the formula (215) is dissolved in 2.0 mlof tricresyl phosphate/methylene chloride (3:7). The methylene chlorideis evaporated off, 6.0 ml of an 8% strength aqueous solution of sodiumisopropylnaphthalene-sulphonate, 20.0 ml of 6% strength gelatinesolution and 3.4 ml of water are added and the mixture is adjusted to pH6.5 and emulsified for 5 minutes by means of an ultrasonic apparatuswith an output of 100 watt.

5.0 ml of coupling agent emulsion freshly treated with ultrasonics, 3.3ml of silver bromide emulsion of pH 6.5, containing 1.4% of silver and6.0% of gelatine, 2.0 ml of 1% strength aqueous solution of the hardenerof the formula ##STR300## and 1.7 ml of water are mixed with one anotherand cast at 40° C. on a substrated glass plate of size 13× 18 cm. Aftersolidifying at 10° C., the plate is dried in a drying cabinet withcirculating air at 32° C.

A strip cut to 4.0 cm × 6.5 cm is exposed to 500 Lux/cm² under a stepwedge for 2 seconds and is subsequently treated at 24° C. as follows:

    ______________________________________                                                           Minutes                                                    ______________________________________                                        1. Colour developing 5                                                        2. Soaking           5                                                        3. First fixing      2                                                        4. Soaking           2                                                        5. Silver bleaching  2                                                        6. Soaking           2                                                        7. Second fixing     2                                                        8. Soaking           2                                                        9. Drying            10                                                       ______________________________________                                    

The processing solutions have the following composition:

    ______________________________________                                        I. Colour developing solution (pH=10.7)                                       4-Amino-3-methyl-N-ethyl-N-β-                                            (methyl-sulphonamido)ethyl-                                                   aniline . 11/2 H.sub.2 SO.sub.4 . H.sub.2 O                                                           10       mmols                                        Anhydrous sodium sulphite                                                                             2.0      g                                            Potassium bromide       0.5      g                                            Potassium carbonate     40.0     g                                            Benzyl alcohol          10.0     g                                            Water                   1,000    g                                            II. Fixing solution (pH=4.5)                                                  Sodium thiosulphate . 6 H.sub.2 O                                                                     80.0     g                                            Anhydrous sodium sulphite                                                                             5.0      g                                            Sodium borate (borax)   6.0      g                                            Potassium alum          7.0      g                                            Acetic acid             4.0      g                                            Water                   1,000    g                                            III. Silver bleach bath (pH=7.2)                                              Potassium ferricyanide  100.0    g                                            Boric acid              10.0     g                                            Sodium borate (borax)   5.0      g                                            Water                   1,000    g                                            ______________________________________                                    

A clear, sharp magenta wedge with an absorption maximum at 540 nm and asubsidiary maximum at 434 nm is obtained.

Analogous results are obtained on using the remaining coupling agentslisted in Tables I to IV.

EXAMPLE II

The strip obtained, and exposed, according to Example I is developed for6 minutes at 24° C. by means of the developer solution specified belowand is rinsed with water at the same temperature.

It is then uniformly exposed to white light and colour-developed asstated in Example I. The strip thus treated gives a clear magenta wedgecorresponding to a colour reversal material.

    ______________________________________                                        IV. Black-and-white developer solution (pH=10.8)                              4-Hydroxy-N-methylaniline . H.sub.2 SO.sub.4                                                            1.0      g                                          Hydroquinone              3.0      g                                          Anhydrous sodium sulphite 50.0     g                                          Sodium carbonate . H.sub.2 O                                                                            25.0     g                                          Potassium thiocyanate     3.6      g                                          Potassium bromide         2.6      g                                          Water                     1,000    g                                          ______________________________________                                    

Analogous results are obtained on using the remaining coupling agentslisted in Tables I to IV or on using the coupling agent of the formula(701).

EXAMPLE III

The casting solution obtained according to Example I using an emulsionwhich is sensitive to green and the coupling agent of the formula (215)is cast on an opaque white acetate film provided with an adhesive layer.On top of this is cast an emulsion sensitive to red, which has beenprepared analogously and contains the coupling agent of the formula(701), and finally an emulsion prepared analogously which contains thecoupling agent of the formula (105).

The material is exposed through a colour-negative film and developed inaccordance with the instructions given in Example I, whereby a clearcolour copy is obtained.

EXAMPLE IV

A solution of 25 mg of the coupling agent of the formula (222) in 1 mlof methylene chloride is emulsified by means of ultrasonics in a mixtureconsisting of 1.6 ml of 6% strength gelatine solution, 2.0 ml ofdistilled water and 1.0 ml of an 8% strength aqueous solution of sodiumdiisobutylnaphthalene sulphonate.

After adjusting the pH value to 6.5, 1.0 ml of a 1% strength aqueoussolution of the hardener from Example I and 1.6 ml of a silver bromideemulsion containing 1.4% of silver are added and the mixture thusobtained is spread by means of a glass rod on a substrated glass plateof size 13× 18 cm. After drying at room temperature, the material isexposed, and developed, as described in Example I. A colour wedge with amaximum density of 1.00 is obtained.

EXAMPLE V

25 mg of the coupling agent of the formula (218) and 50 mg of acopolymer consisting of 50 parts of styrene and 50 parts of ethylacrylate are dissolved in 1.2 ml of methylene chloride and this solutionis dispersed, and cast with an emulsion, as described in Example IV.After drying, the material is exposed, and developed, as described inExample I. A colour wedge of maximum density 0.78 is obtained.

What we claim is:
 1. Colour-photographic recording material with atleast one light-sensitive silver halide emulsion layer which contains atleast one colour coupler having an active methylene group or a phenolichydroxyl group and containing at least one radical of a phosphonic aciddiester, phosphonic acid diamide or phosphonic acid ester amide. 2.Photographic material as claimed in claim 1 which contains a colourcoupler of the formula ##STR301## wherein W₁ denotes an alkyl radical orbenzene radical,Q₁ denotes a radical which can be split off duringcolour coupling, A₁ denotes a benzene radical, M₁ denotes a direct bond,an oxygen atom or one of the atom groupings alkyl

    --N--

(of which the alkyl group contains at most 4 carbon atoms), --CO--HN--,NH--OC--, --CO--O, --CO--HN--benzene radical and --NH--OC--benzeneradical, L₁ denotes an oxygen atom, an alkylene group, a cyclohexaneradical, a benzene radical or an aralkylene radical, but only one of thesymbols M₁ and L₁ can represent an oxygen atom, R₁ denotes an alkylgroup with 2 to 18 carbon atoms, R'₁ denotes an alkyl group with 2 to 8carbon atoms or an alkoxy group with 2 to 18 carbon atoms or R₁ and R'₁together denote an -O-alkylene- group and n denotes one of the numbers 1and
 2. 3. Photographic material as claimed in claim 1 which contains acolour coupler of the formula ##STR302## wherein M₁, L₁ and n have theindicated meaning,W₂ denotes a tertiary butyl radical, a benzene radicalwhich is not substituted further or a benzene radical which issubstituted further by at least one of the substituents alkyl with atmost 4 carbon atoms, methoxy, ethoxy, chlorine or benzoylamino, Q₂denotes one of the radicals of the formulae --H, --Cl.
 4. Photographicmaterial as claimed in claim 1 which contains a colour coupler of theformula ##STR303## wherein W₂, Q₂, A₂, R₂, R'₂ and n have the indicatedmeaning,M₂ denotes a direct bond, an oxygen atom or one of the atomgroupings --CO--HN--, --NH--OC--, --CO--HN--benzene radical or--NH--OC--benzene radical, and L₂ denotes an oxygen atom, an alkylenegroup with 1 to 3 carbon atoms, a benzene radical or an aralkyleneradical, with the proviso that M₂ does not present oxygen, --CO--HN-- or--HN--CO-- if L₂ represents an oxygen atom, and n can only be 2 if M₂ isa --CO--HN--benzene radical or --NH--OC--benzene radical. 5.Photographic material according to claim 4 which contains a colourcoupler of the formula ##STR304## wherein Q₂, A₂, M₂, L₂, R₂, R'₂ and nhave the indicated meaning.
 6. Photographic material according to claim4 which contains a colour coupler of the formula ##STR305## wherein Q₂,A₂, M₂, L₂, R₂, R'₂ and n have the indicated meaning andW₃ denotes abenzene radical which is not substituted further or a benzene radicalwhich is substituted further by at least one of the substituents alkylwith at most 4 carbon atoms, methoxy, ethoxy, chlorine or benzoylamino.7. Photographic material as claimed in claim 1 which contains a colourcoupler which corresponds to one of the formulae ##STR306## 8.Photographic material according to claim 1 which contains a colourcoupler of the formula ##STR307## wherein G₁ denotes a benzeneradical,Q₁ denotes a radical which can be split off during colourcoupling, U₁ denotes a hydrogen atom, a chlorine atom, an alkali groupwith at most 4 carbon atoms or an alkoxy group with at most three carbonatoms, R₁ denotes an alkyl group with 2 to 18 carbon atoms, n denotesone of the numbers 1 and 2 and t denotes one of the numbers 3 and
 5. 9.Photographic material as claimed in claim 8 which contains a colourcoupler of the formula ##STR308## wherein G₂ denotes a benzene radicalwhich is not substituted further or is substituted further by at leastone of the substituents chlorine, methyl, methoxy or phenoxy andR₂denotes an alkyl group with 2 to 8 carbon atoms and n has the indicatedmeaning.
 10. Photographic material as claimed in claim 9 which containsthe colour coupler of the formula ##STR309##
 11. Photographic materialaccording to claim 1 which contains a colour coupler of the formula##STR310## wherein Q₁ denotes a radical which can be split off duringcolour coupling,D₁ denotes a benzene radical which is not substitutedfurther or a benzene radical which is substituted further by at leastone of the substituents halogen, nitrile, lower alkyl (which can itselfcarry further substituents), lower alkoxy, lower alkylsulphonyl oracylamino with 1 to 28 carbon atoms, T₁ denotes an acylamino group, aphenylureido group, a phenylamino group which is not substituted furtheror is substituted further by at least one of the substituents halogen,lower alkyl, lower alkoxy or acylamino with 1 to 28 carbon atoms or (ifn= 2) a direct bond, R₁ denotes an alkyl group with 2 to 18 carbonatoms, m and n each denote one of the numbers 1 and 2, p denotes one ofthe numbers 1, 2 and 3 and r denotes an integer of value at most
 18. 12.Photographic material as claimed in claim 11 which contains a colourcoupler of the formula ##STR311## wherein D₂ denotes a benzene radicalwhich is optionally substituted further by one or more chlorine atoms,methyl groups or methoxy groups and/or by a nitrile group,R₂ denotes analkyl group with 2 to 8 carbon atoms, k, m and s each denote one of thenumbers 1 and 2 and t denotes one of the numbers 3 and
 5. 13.Photographic material as claimed in claim 11 which contains a colourcoupler of the formula ##STR312## wherein R₃ denotes a n-butyl or2-ethylhexyl group,Y denotes a chlorine atom, a methyl group or methoxygroup, Y' denotes a chlorine atom or a methyl group, k and s each denoteone of the numbers 1 and 2 and t denotes one of the numbers 3 and
 5. 14.Photographic material according to claim 11 which contains a colourcoupler of the formula ##STR313## wherein D₂, R₂, m and t have theindicated meaning andV₁ denotes a hydrogen atom or a chlorine atom. 15.Photographic material according to claim 14 which contains a colourcoupler of the formula ##STR314## wherein Y, Y', R₃ k and t have theindicated meaning.
 16. Photographic material according to claim 1 whichcontains a colour coupler of the formula ##STR315## wherein R₁, R₂, V₁,m, p and r have the indicated meaning.
 17. Photographic materialaccording to claim 16 which contains a colour coupler of the formula##STR316## wherein R₃, k, m and t have the indicated meaning. 18.Photographic material according to claim 17 which contains a colourcoupler of the formula ##STR317## wherein R₃, k and t have the indicatedmeaning.
 19. Photographic material according to claim 18 which containsa colour coupler of the formula ##STR318##
 20. Photographic materialaccording to claim 1 which contains a colour coupler of the formula##STR319## wherein Q₁, R₁, p and r have the indicated meaning. 21.Photographic material according to claim 20 which contains a colourcoupler of the formula ##STR320## wherein V₁, R₂ and k have theindicated meaning.
 22. Photographic material according to claim 21 whichcontains a colour coupler of the formula ##STR321##